Azo-dyestuffs



Patented June 23, 1936 oNiTEo STATES PATENT OFFICE AZO-DYESTUFFS Friedrich Felix and Wilhelm Huber, Basel, Switzerland, assignors to Society of Chemical Industry in Basic, Basel, Switzerland No Drawing. Original application June 8, 1933,

Serial No. 674,966. Divided and this application July 10, 1935, Serial No. 30,738. In Switzerland July 9, 1932 13 Claims. (Cl. 260-96) 10 group, wherein R1 stands for hydrogen, alkyl, aralkyl or acidyl, R2 for an aliphatic hydrocarbon radical consisting of at least two carbon atoms, and R3 for acyl. Here and throughout the specification alkyl not only means the homologues of 15 the CH3- and czHs-groups, but also the substituted radicals thereof, such as C2H4C1, C2H4N(CH3) 2, C2H4sO3H, and soforth. The term alkyl comprises also radicals with double bonds,

such as, for example, the allyl radical. The

to process may consist in causing a diazo-compound of an aromatic base to react with a coupling component which contains at least one w-acyl-oxalkylamino-group. Another 'form of the process consists in substituting in an aminoaZo-dyestufi the 25 primary or secondary amino-group by subsequent treatment with an ester of an alcohol which stiil contains at least one group capable of reacting with the primary or secondary amino-group of the dyestuff.

30 This may be done, for example, by causing the dyestuff which contains a primary or secondary amino-group to react with an aryl-sulfonic acid ester or sulfonic acid ester of a polyhydric alcohol with 2 or more C-atoms containing an Ol-I-group 35 which is esterified with an organic acid. Further, the hydrogen halide acid ester of the partially with an organic acid esterified polyhydric alcohol may be used. Further, in the case of dyestufis having w-oxalkylaminogroups which are obtain- 40 able by means of compounds, such as OH OH these groups can be esterified with an organic acid; or dyestufis which contain an w-halogenalkylamino-group, for instance a 50 treated with the salt of an organic acid, such as sodium formate or sodium acetate.

The dyestuffs thus obtained have the general formula 55 AN=NB-N Rr-o-Ri wherein A and B stand for nuclei of the benzene or naphthalene series, and R1, R2 and R3 have the 60 meanings already indicated above. These dyestuffs form yellow, orange, brown, red, violet, blue or black powders, and dissolve in solvents, such as water (if the dyestulfs contain sulionic groups capable of forming alkali salts), or acetic ester or glacial'acetic acidor pyridine (if the dyestuffs 5 contain no SO3H-group or COOH-group) to yellow, orange, brown, red, violet, blue or black solw tions. They dye textiles, such as wool, silk, cotton, artificial silk from regenerated cellulose,

cellulose esters and cellulose ethers and artificial silk consisting of such materials, in the shades indicated above.

As hereinbefore mentioned these dyestuffs may be obtained by combining any diazotizing components with such coupling components which contain the group wherein R1, R2 and R3 have the meanings already indicated above. In this case there may be used as diazotizing components aniline, toluidine, nitraniline, particularly para-nitraniline, chloraniline or a sulfonlc or carboxylic acid of any of these, for instance sulfanilic acid, metanilic acid or the like, nitrochloraniline, particularly 2-chloro-4-nitraniline, 2,6-dichloro-4- nitraniline, anisidine, nitroanisidines and chloroanisidines, particularly l-nitro-ortho-anisidine; dinitroanilines, particularly 2,4-dinitraniline, dinitrochloro-anilines, particularly 2,4-dinitro-6- chloraniline; ortho-aminophenol or its homologues and analogues, suchas ortho-aminocresols, nitroaminophenols, particularly 5-nitro-orthoaminophenol, chloro-aminophenols and their sulfonic acids, naphthylamines, naphthylamine sulfonic acids, such as 1,8-amino-naphthol sulfonic acid, 1,8-aminonaphthol-3,fi-disulfonic acid,

or the toluene-sulfonic acid esters thereof;

aminoazobenzene and its homologues and analogues, such as aminoazotoluene aminoazobenzene-sulfonicacids, aminoazo-dyestufis, such as the azo-dyestuff from 1 mo1. 0f diazotized aniline sulfonic acid or naphthylamine sulfonic acid and one mol. of a middle component, such as aniline, cresidine, u-naphthylamine, a-naphthylamine-fior 7-sulfonic acids, 1-amino-2-methoxynaphthalene, and so forth, or still more complicated diam-compounds, as illustrated below. i

With the diazotizing components just mentioned there are suitable as coupling components any bases, capable of coupling, which contain at the nitrogen atom, for instance, an (ii-acyloxalkyl residue, for instance N(w-acetoxyethyl)- aniline or N-ethyl-N(w-acetoxyethyl) -aniline of the formula V om-onr-ooo-on,

or N(w-acetoxyethyl) -toluidin es or -anisidines, N -methyl-N wv acetoxyethyl) -aniline, -toluidines or anisidines.

The organic esters of aryl-aminoalcohols may be made, for example, by condensing the corresponding amine, such as aniline, ethylaniline, 1- amino-2-methoxy-5-methyl-benzene or the like, with an organic ester of a polyhydric alcohol,

which contains only one non-esterified hydroxylr group, or by treatment with their sulfuric acid esters or arylsulfonic acid esters. They may also. be obtained by condensing an organic ester of a halogenated alcohol with the amine or advantageously by esterifying the corresponding arylamino-alcohol with an organic acid, or'b'y causing an arylaminohalogenalkyl, compound to react with'a salt of an organic acid, for instance with an alkali acetate or formate, or, finally, by reaction between an aryl-compound which contains in the nucleus a substituent capable of reaction, for instance a halogen in ortho-position.

acetoxyethyl) -aniline; red to Bordeaux-red tints by coupling para-nitraniline, 4-nitro-ortho-anisidine or 2-chloro-4-nitraniline with N-ethyl- Nfl i-acetoxyethyl) -aniline.

The following examples illustrate the invention, the parts being by weight:

Ezvample 1 to the nitro-group, and an organic ester of an aminoalcohol.

The dyestuffs of the above general formula may also be obtainedif the diazotizing component contains the characteristic V group, wherein R1, R2 and R3 have the meanings already indicated above. Such methods of producing these dyestuffs are described further below and are. illustrated by examples.

As already mentioned these dyestufis may be used for dyeing textiles of Various kinds. They can of course also be used for other purposes, for examplaas pigments, for dyeing lacquers and varnishes, for dyeing paper, and 'so forth. They can also be used as intermediate products for the production of further azo-dyestuffs, and if required fonthe production of further dyestuffgroups. l

The non-sulfonated dyestuffs are in particular used for 'dyeing esters and ethers of cellulose, and when brought into suitable form or suspended in a suitable mediurn, have a pronounced aflinity for cellulose esters and'ethers, particula rly'acetafte silk, which they dye very fast tints.

The non-sulfonateddyestui fs may bebrought into a finely sjubdivided form for example by grinding them with a" dispersing agent, such as the sulfonated residue fr orn the manufacture of benzaldehyde, a turpentine oil or the like, in the presence of water to produce a fine paste, or they may be converted in presence of further quantitles of the aforesaid. or other; auxiliary substances, for example sulfitecellulose waste liquor byIcautiously drying them preferably in a vacuumfat'a. temperature not too high, intod ry puli bl i ce-mean The following may further be mentioned for dyeing acetate-silk:-

Yellow to orange tints are. obtained-by coupling aniline or para -nitraniline with Nugis filtered and washed. It is a red powder which, when reduced to a fine state of subdivision by a suitable addition, dyes acetate silk intense fast scarlet red tints. The N-ethyl-N(w-acetoxy ethyl),-aniline used in this example may be made, for instance as follows:-

parts of N-ethyl-N (w-hydroxyethyl) -am'line are mixed with 1 molecular proportion of acetic anhydride and 1 molecular proportion of anhydrous sodium acetate, whereupon reaction be gins with an intense development of heat. When the reaction is at an end, the mass is distilled in a vacuum and there is obtained the N-ethyl- N(w-acetoxyethyl)-aniline of the formula in the form of an oil as clear as Water, and boiling at 126 C. under 2' mm. pressure; the yield is good.

Example 2 The diazo-solution made in the usual manner from 16.8 parts of nitro-or-tho-anisidine is mixed with 13.6 parts ofcrystallized sodium acetate and added to a solution of 20.7 parts of N-ethyl-N(w-acetoxyethyl)-aniline in dilute hydrochloric acid. The dyestuff thus obtained of the formula CHr-OHz-O-OO-OHa is a dark red powder which dyes acetatesilk fast red tints.

Example 3 17.25 parts of 2-chl0ro-4-nitraniline are ground with Water and diazotized by means of 25 parts of concentrated hydrochloric acid and 7 parts of sodium nitrite. The diazo-solution thus obtained is mixedwith 13.6 parts of crysr tallized sodium acetate. and allowed to flow into parts of N -e,thyl -N w-acetoxya solution of 20.7

ethyl) -aniline in dilute hydrochloric acid. "The dyestuff of the formula 0 NO N: N

dissolve in solvents to yellow, orange, brown, red, violet, blue or black solutions, and dye textiles separates in the form of a red-violet powder; it dyes acetate silk magnificent bluish-red tints.

Example 4 19.5 parts of sodium sulfanilate are dissolved in 200 parts of water and the solution is diazotized by means of 7 parts of sodium nitrite and 25 parts of concentrated hydrochloric acid. This diazo-solution is mixed with a solution of 20.7 parts of N-ethyl-N(w-acetoxyethyl)-ani1ine. The dyestuff thus obtained of the formula V Y OHz-CHn-O-C O-GHa dyes wool in an acid bath orange-yellow tints. It may be used for producing printingeffects on acetate silk.

Example 5 Into a solution of 20.? parts of N-ethyl-Nuiiacetoxyethyl) -aniline in dilute hydrochloric acid there is allowed to flow a diazo-solution prepared in known manner from 20.? parts of 2:6-dichlorol-nitroaniline. When coupling has been completedby the addition of sodium acetate the dyestuff of the formula CiHs NO: N=N- N\ v CHrCHrCFC CBQ C] which has separated, is filtered. It is a dark brown powder, soluble in ethyl acetate to a yellow-brown solution and capable of dyeing acetate silk yellow-brown tints, which can be discharged to a pure white.

Example: 6

5 CHz-OHr-O-C O-GHs separates in the form of a dark powder. It dyes acetate artificial silk vivid red tints.

What we claim is:- 1. Azo-dyestufis of the general formula R1 AN=NB-N \R -OR wherein A and B stand for nuclei of the benzene or naphthalene series, R1 stands for hydrogen or an alkyl-group, R2 stands for an aliphatic hydrocarbon radical consisting of at least two carbon atoms, and R3 stands for an acyl-group consisting of at least one and not more than two carbon atoms, which products form yellow, orange, brown, red, violet, blue or black powders,

similar shades. V 1

2. Azo-dyestuffs of the general formula AN=NB-N CHz-CHrO-R:

wherein A and B stand for nuclei of the benzene ornaphthalene series, R1 stands for hydrogen or an alkyl-group, and R3 stands for an acyl-group consisting of at least one and not more than two carbon atoms, which products form yellow, orange, brown, red, violet, blue or black powders, dissolve insolvents to yellow, orange, brown, red, violet, blue or black solutions, and dye textiles similar shades.

3. Monoazo-dyestuffs of the general formula AN=NBN/ CHr-CH2-O-R:

wherein A and B standfor nuclei of the benzene or naphthalene series, R1 stands for hydrogen or an alkyl-group, and Re stands for an acyl-group consisting of at least one and not more than two carbon atoms, which products form yellow, orange, brown, red, violet or blue powders, dissolve in solvents to yellow, orange, brown, red, violet or blue solutions, and dye textiles similar shades.

4. Unsulfonated monoazo-dyestuffs of the general formula wherein A and Bstand for nuclei of the benzene or naphthalene series,'R1 stands for hydrogen or an alkyl-group, and R3 standsfor an acyl-group consisting of at least one and not more than two carbon atoms, which products form yellow, orange, brown, red, violet or blue powders, dissolve in acetic ester to yellow, orange, brown, red, violet or blue solutions, and dye acetate artificial silk similar shades.

5. Unsulfonated monoazo-dyestuffs of the general formula wherein A stands for a benzene nucleus, B stands for a nucleus of the benzene or naphthalene series, R1 stands for hydrogen or an alkylgroup, and R3 stands for an acyl-group consisting of at least one and not more than two carbon atoms, which products form yellow, orange, brown, red, violet or blue powders, dissolve in acetic ester to yellow, orange, brown, red, violet or blue solutions, and dye acetate artificial silk similar shades.

6. Unsulfonatedmonoazo-dyestuffs of the general formula RI AN=NB-N/ CHrCHg-()R;

wherein A stands for a benzene nucleus carrying a nitro-group in para-position to the N=N- o p B tand tor a nuc u hi th benzene or naph h n eri s R1, stands p ydro en ran alkyl-group, and R3 stands for an acyl-group consisting of at least one and not more than two carbon atoms, which products form orange, brown, red, violet or blue powders, dissolve in acetic ester to orange, brown, red, violet or blue solutions, and dye acetate artificial silk similar shades.

7. Unsulfonated monoazo-dyestuffs of the general formula alkyl wherein A and B stand for nuclei of the benzene series, the nucleus A carrying a nitro-g-roup in para-position to the N=Ngroup, and R3 stands for an acyl-group consisting of at least one and not more than two carbon atoms, which products form orange, brown, red or violet powders, dis, solve in acetic ester to orange, brown, red or violet solutions, and dye acetate artificial silk similar shades.

8. Unsulfonated monoazo-dyestufis of the general formula alkyl CHrCHrO-CO-CHZI wherein A and B stand for nuclei of the benzene series, the nucleus A carrying a nitro-group in para-position to the .N=Ngr oup, Which products form scarlet, red or violet powders, dissolve in acetic ester to scarlet, red or violet solutions, and dye acetate artificial silk similar shades.

9. Unsulfonated mon'oazo-dyestuifs of the general formula onr-oriwoaoo-em wherein A and B stand for nuclei of the benzene series, the nucleus A carrying a nitro-group in para-position to the N:N-group, which prod;-

ucts form scarlet, red or violet powders, dissolve nia ti zestsrto scarlet, red or Violet solutions, and dye acetate artificial silk similarshades.

10. Unsulfonated monoazo-dyestuffs of the general formula V which product forms a scarlet-red powder, dissolves in acetic ester to a scarlet, red solution and dyes acetate artificial silk fast scarlet shades.

12. The non-'sulfonated monoazo-dyestufi of the formula CHr-C'HrO-ClO-CH; which product forms a dark powder, dissolves in acetic ester to a blue-red solution, and dyes acetate artificial silk pure blue-red shades.

13. The non-sulfonated' monoazoedyestufi of the formula which product forms a dark powder dissolves in acetic ester to a redsolution and dyes acetate artificial silk red shades.

' FRIEDRCECH FELIX.

WI-LHELM HUBER. 

